Novel Polymers

ABSTRACT

The present invention relates to polymers comprising repeating unit(s) of the formula (I), and their use in electronic devices. The polymers according to the invention have excellent solubility in organic solvents and excellent film-forming properties. In addition, high charge carrier mobilities and high temperature stability of the emission color are observed, if the polymers according to the invention are used in polymer light emitting diodes (PLEDs).

The present invention relates to novel polymers comprising repeatingunit(s) of the formula I and their use in electronic devices. Thepolymers according to the invention have excellent solubility in organicsolvents and excellent film-forming properties. In addition, high chargecarrier mobilities and high temperature stability of the emission colorcan be observed, if the polymers according to the invention are used inpolymer light emitting diodes (PLEDs).

JP11092420 relates to triphenylene derivatives of the formula

wherein Ar₁ to Ar₆ are each an aryl or the like; R₁₁ to R₁₆ are eachformula

(R₁ to R₃ are each, for example, H); R₂₁ to R₂₆ are each, for example,an alkyl; m1-m6 are each 0 or 1; n1-n6 are each 0, 1, or 2, which areuseful as a liquid crystalline material. The following compounds areexplicitly disclosed:

R═Cl, Br, or F.

JP2006143845 relates to compounds of formula

wherein Z₁, Z₂ are an aromatic hydrocarbon ring, aromatic heterocyclicring; R₁ to R₃ are H, substituent; n1=0 to 3; n2, n3=0 to 4; L1=linkagegroup, single bond). The compounds show high luminescence efficiency andlong service life. The followingcompound

is used as starting material for the preparation of the above compounds.

WO2006038709 compounds represented by the general formula

wherein R₁ to R₆ are each independently hydrogen or substituentrepresented by the general formula —C≡CSiRaRbRc, with the proviso thatat least one of R₁ to R₆ is a substituent represented by the generalformula —C≡CSiRaRbRc, wherein Ra, Rb, Rc are each independently anC₁-C₁₀ aliphatic hydrocarbon group or aromatic hydrocarbon group. Thecompounds are prepared by coupling of halogenated triphenylenecompounds.

(X₁ to X₆ are each independently H, Br, or iodo, with the proviso thatat least one of X1-X6 is Br or iodo) with a silylacetylene of generalformula HC≡C SiRaRbRc (Ra, Rb, Rc=same as above). An organicelectroluminescent device comprising a luminescent layer containing atleast one of compounds of formula

and a phosphorescent dopant is also disclosed. A compound of formula

is explicitly disclosed, wherein X₁ to X₆ are each Br.

US2005025993 relates to ectroluminescent devices which comprise ananode; a cathode; a first organic layer disposed between the anode andthe cathode, where the first organic layer comprises a material thatproduces phosphorescent emission when a voltage is applied between theanode and the cathode; and a second organic layer disposed between thefirst organic layer and the cathode, where the second organic layer isin direct contact with the first organic layer, and where the secondorganic layer comprises a nonheterocyclic aromatic hydrocarbon material,such as, for example,

US2004209117 relates to an EL device, comprising an azole compound ofthe formula

wherein Y is an atom or a group selected from the group consisting of O,S, and —N(R)—, wherein R is a hydrocarbyl group of from 1 to about 30carbons; Z¹ and Z² are each a substituent selected from the groupconsisting of hydrogen, an alkyl group of from 1 to about 25 carbonatoms, an aryl group of about 6 to about 30 carbon atoms, an alkoxygroup of from 1 to about 25 carbon atoms, a halogen, and a cyano group;and Ar is an aromatic component. JP2004161892, JP2002050473 andJP2001023777 disclose phenanthroimidazol compounds and their use in ELdevices.

WO04/030029 relates to a photovoltaic EL cell, comprising polymerscontaining groups:

WO03/020790 relates to conjugated polymers comprising spirobifluoreneunits. The polymers can comprise repeating units derived from thefollowingcompound

EP0757035A1 relates to phenanthrylenediamine derivatives represented bythe general formula

which are excellent in the electric charge transferring capability, thecompatibility with a binding resin and the stability, thereby providinga photosensitive material which is highly sensitive and excellent in thedurability.

US2001008711 relates to an organic light-emitting device comprising alight-emitting layer or a plurality of organic compound thin layersincluding a light-emitting layer formed between a pair of electrodes,wherein at least one layer comprises at least one kind of compoundrepresented by the following formula NR₁₁R₁₂R₁₃: wherein R₁₁, R₁₂ andR₁₃ each represents a group having a cyclocondensed polycyclichydrocarbon structure in which three or more rings are cyclocondensed;and a novel cyclocondensed polycyclic hydrocarbon compound.

US2004/0028944 relates to organic electroluminescent devices comprisinga triarylamine derivative represented by the general formulaN(Ar₁)(Ar₂)(Ar₃), wherein Ar₁ to Ar₃ are substituted or unsubstitutedaryl groups and at least one of Ar₁ to Ar₃ is a 9-phenanthryl group.

EP1440959A1 relates to a novel soluble compound of formula

wherein Ar₃ represents a substituted or unsubstituted anthracendiylgroup, or a substituted or unsubstituted fluorendiyl group and to itsuse in an electroluminescent device.

WO03/064373 relates to triarylamine derivatives and the use thereof ashole transport material in organic electroluminescent andelectrophotographic devices.

WO04/005288 relates to charge transport compositions comprising aphenanthroline derivative having formula

wherein: R₁ and R₂ are the same or different at each occurrence and areselected from H, F, Cl, Br, alkyl, heteroalkyl, alkenyl, alkynyl, aryl,heteroaryl, C_(n)H_(a)F_(b), OC_(n)H_(a)F_(b), C₆H_(c)F_(d), andOC₆H_(c)F_(d); a, b, c, and d are 0 or an integer such that a+b=2n+1,and c+d=5, n is an integer; x is 0 or an integer from 1 through 3; y is0, 1 or 2; with the proviso that there is at least one substituent on anaromatic group selected from F, C_(n)H_(a)F_(b), OC_(n)H_(a)F_(b),C_(g)H_(c)F_(d), and OC₆H_(c)F_(d).

WO05/014689 relates to conjugated polymers containingdihydrophenanthrene units of formula

and their use in polymer organic light emitting diodes.

WO05/104264 relates to polymers comprising structural units of formula

wherein both groups R among others can form together a mono- orpolycyclic, aliphatic ring system.

WO07/017,066, which enjoys an earlier priority date than the present,but has been published after the priority date of the present inventionrelates to polymers comprising structural units of formula

wherein both groups R among others can form together a mono- orpolycyclic, aromatic aliphatic ring system.

WO2005030828 relates to polymers comprising repeating units of formula

wherein X is CR₂, N(R¹), —CR₂—CR₂—, or —N(R¹)—CR₂— and Z is CR, or N.The polymers have high solubility, exhibit an excellent air-stabilityand a low voltage rise during longer operation when used in a polymerorganic light-emitting diode (PLED).

There are a number of challenges faced with the introduction of organicEL displays when their performance is compared with existingtechnologies. Obtaining the exact color coordinates required by specificguidelines (i.e. NTSC) has been problematic. The operational lifetime ofthe EL device is still lower when contrasted to the existing inorganictechnology for cathode ray tubes (CRTs) and liquid crystal displays(LCDs). In addition, producing a material with a pure blue color and along lifetime is one of the greatest problems for this industry.

Accordingly, it is the object of the present invention to provide novelmaterials, which show significant advantages in color purity, deviceefficiency and/or operational lifetime, when incorporated inelectro-optical devices.

Said object is solved by the polymers of the present inventioncomprising repeating units of formula I. Organic light emitting devices(OLEDs), comprising the polymers of the present invention, can showsignificant advantages in color purity, device efficiency and/oroperational lifetime. In addition, the polymers can have good solubilitycharacteristics and relatively high glass transition temperatures, whichfacilitates their fabrication into coatings and thin films, that arethermally and mechanically stable and relatively free of defects. If thepolymers contain end groups which are capable of being crosslinked, thecrosslinking of such groups after the films or coating is formedincreases the solvent resistance thereof, which is beneficial inapplications wherein one or more solvent-based layers of material aredeposited thereon.

Hence, the present invention relates to polymers comprising repeatingunit(s) of the formula

whereinR¹, R², R³, R⁴, R⁵, R⁶ and are independently of each other hydrogen, F,SiR¹⁰⁰R¹⁰¹R¹⁰², or an organic substituent, orR¹ and R³, R⁴ and R², R³ and R⁴, and/or any of the substituents R⁵and/or R⁶, which are adjacent to each other, together form an aromatic,or heteroaromatic ring, or ring system, which can optionally besubstituted, m is 0, or an integer of 1 to 3,n1 and n2 are 0, or an integer 1, or 2,R¹⁰⁰, R¹⁰¹ and R¹⁰² are independently of each other C₁-C₁₈alkyl,substituted or unsubstituted C₆-C₁₈aryl, andAr¹ and Ar² are each independently of each other a substituted orunsubstituted arylen, or heteroarylen group, such as a substituted orunsubstituted phenylene group, a substituted or unsubstitutednaphthalene group, a substituted or unsubstituted anthracene group, asubstituted or unsubstituted diphenylanthracene group, a substituted orunsubstituted phenanthrene group, a substituted or unsubstitutedacenaphthene group, a substituted or unsubstituted biphenylene group, asubstituted or unsubstituted fluorene group, a substituted orunsubstituted carbazolyl group, a substituted or unsubstituted thiophenegroup, a substituted or unsubstituted triazole group or a substituted orunsubstituted thiadiazole group.

The polymers of the present invention should have a glass transitiontemperature above 100° C., especially a glass transition temperatureabove 150° C.

R¹ and R² as well as R³ and R⁴ can be different from each other, but arepreferably the same. R¹, R², R³ and R⁴ are preferably selected fromC₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₁-C₁₈perfluoroalkyl and are most preferred an optionally substitutedC₆-C₂₄aryl, or C₂-C₂₀heteroaryl group.

In a preferred embodiment of the present invention at least one, veryespecially at least two of R¹, R², R³ and R⁴ are different from H. Mostpreferred all of the substituents R¹, R², R³ and R⁴ are different fromH. In another preferred embodiment of the present invention at leastone, preferably two of the substituents R¹, R², R³ and R⁴ are anoptionally substituted C₆-C₂₄aryl, or C₂-C₂₀heteroaryl group. Mostpreferred all of the substituents R¹, R², R³ and R⁴ are an optionallysubstituted C₆-C₂₄aryl, or C₂-C₂₀heteroaryl group.

Preferably, the polymer of the present invention comprises repeatingunit(s) of formula I, wherein R¹ and R² are independently of each otherH, F, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, C₁-C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which issubstituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G;

R³ and R⁴ are independently of each other H, F, C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, C₁-C₁₈perfluoroalkyl,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G; wherein especially at leastone, very especially at least two of R¹, R², R³ and R⁴ are differentfrom H; wherein especially at least one, very especially at least two ofR¹, R², R³ and R⁴ are different from H, each group R⁵ and R⁶ isindependently of each other in each occurrence H, halogen, especially F,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₁-C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted byG, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, C₇-C₂₅aralkyl, CN, or —CO—R²⁸,m is 0, or an integer 1 to 3,D is —CO—; —COO—; —S—; —SO—; —SO₂—; —O—; —NR²⁵—; —SiR³⁰R³¹—; —POR³²—;—CR²³═CR²⁴—; or —C≡C—; andE is —OR²⁹; —SR²⁹; —NR²⁵R²⁶; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁶; —CN; orhalogen, especially F;G is E, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is interrupted by D,C₁-C₁₈perfluoroalkyl, C₁-C₁₈alkoxy, or C₁-C₁₈alkoxy which is substitutedby E and/or interrupted by D,R²³, R²⁴, R²⁵ and R²⁶ are independently of each other H; C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—;R²⁷ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; especially C₁-C₁₈alkyl; or C₁-C₁₈alkyl which isinterrupted by —O—,R²⁸ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,R²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl,or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by—O—,R³⁰ and R³¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl, orC₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, andR³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl.

In an especially preferred embodiment the polymers contain repeatingunits of formula

wherein R¹, R² and R³ are independently of each other C₆-C₁₂aryl, orC₂-C₁₁heteroaryl, which may optionally be substituted by one or moregroups G, wherein G is as defined above, and R⁴ has the meaning of R³,or is C₁-C₁₈alkyl, especially C₄-C₁₈alkyl. Polymers are even morepreferred, which contain repeating units of formula (IIa), wherein R¹,R² and R³ are independently of each other

wherein n₁ is 0, or an integer 1, 2, 3, or 4, especially 0, 1, or 2; n₂is 0, or an integer 1, 2, or 3, especially 0, 1, or 2; n₃ is 0, or aninteger 1, 2, 3, 4, or 5, especially 0, 1, 2, or 3; and R¹⁰ and R¹¹ areindependently of each other C₁-C₂₅alkyl, or C₁-C₂₅alkoxy, and R⁴ has themeaning of R³, or is C₁-C₁₈alkyl, especially C₄-C₁₈alkyl.

Preferably, R⁵ and R⁶ are independently of each other H, C₁-C₁₈alkyl,such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl,sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl,2-ethylhexyl, or n-heptyl; C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, such as —CH₂OCH₃, —CH₂OCH₂CH₃, —CH₂OCH₂CH₂OCH₃, or—CH₂OCH₂CH₂OCH₂CH₃; C₁-C₁₈alkoxy, such as methoxy, ethoxy, n-propoxy,iso-propoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, 2-methylbutoxy,n-pentyloxy, isopentyloxy, n-hexyloxy, 2-ethylhexyloxy, or n-heptyloxy;C₆-C₁₄aryl, such as phenyl, naphthyl, or biphenylyl, C₅-C₁₂cycloalkyl,such as cyclohexyl, C₆-C₁₄aryl which is substituted by G, such as—C₆H₄OCH₃, —C₆H₄OCH₂CH₃, —C₆H₃(OCH₃)₂, or —C₆H₃(OCH₂CH₃)₂, —C₆H₄CH₃,—C₆H₃(CH₃)₂, —C₆H₂(CH₃)₃, —C₆H₄OtBu, or —C₆H₄tBu. Most preferred R⁵ andR⁶ are H.

m is preferably 0, 1 or 2. If more than one group R⁵, or R⁶ is presentwithin one molecule, they can have different meanings.

D is preferably —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NR²⁵—, wherein R²⁵is C₁-C₁₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, or sec-butyl, or C₆-C₁₄aryl, such as phenyl, naphthyl, orbiphenylyl.

E is preferably —OR²⁹; —SR²⁹; —NR²⁵R²⁵; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁵; or—CN; wherein R²⁵, R²⁷, R²3 and R2⁶⁹ are independently of each otherC₁-C₁₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C₆-C₁₄aryl, suchas phenyl, naphthyl, or biphenylyl.

G has the same preferences as E, or is C₁-C₁₈alkyl, especiallyC₁-C₁₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, sec-butyl, hexyl, octyl, 1-(2-hexyl)-decane, or 2-ethyl-hexyl.

Examples of especially preferred polymers, comprising repeating unit(s)of formula (IIa) are shown below:

R¹ R² R³ R⁴

″ ″

″ ″ tBu

″ ″

″ ″

tBu

The monomers for the preparation of the polymers of the presentinvention are new and form a further embodiment of the presentinvention. Accordingly, the present invention is also directed tomonomers of the formula

wherein Ar¹, Ar², n₁, n₂, R¹, R², R³, R⁴, R⁵, R⁶ and m are as definedabove. X¹¹ is independently in each occurrence a halogen atom,especially I, Cl, or Br; —ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ andR²⁰⁹ are identical or different and are H or C₁-C₆alkyl, wherein tworadicals optionally form a common ring and these radicals are optionallybranched or unbranched and X¹² is a halogen atom, very especially I, orBr; or —OS(O)₂CF₃, —OS(O)₂-aryl, especially

—OS(O)₂CH₃, —B(OH)₂, —B(OY¹¹)₂,

—BF₄Na, or —BF₄K, wherein Y¹¹ is independently in each occurrence aC₁-C₁₀alkyl group and Y¹² is independently in each occurrence aC₂-C₁₀alkylene group, such as —CY¹³Y¹⁴—CY¹⁵Y¹⁶—, or—CY¹⁷Y¹⁸—CY¹⁹Y²⁰—CY²¹Y²²—, wherein Y¹³, Y¹⁴, Y¹⁵, Y¹⁶, Y¹⁷, Y¹⁸, Y¹⁹,Y²⁰, Y²¹ and Y²² are independently of each other hydrogen, or aC₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, or —C(CH₃)₂CH₂C(CH₃)₂—,with the proviso that the following compounds are excluded:

Y² Y³ Y⁵ Y⁶ Y⁷ Y⁸ Y⁹ Y¹⁰ Y¹¹ Y¹² (CH₂)₅Me (CH₂)₅Me H H Br H H Br H H OMeOMe OAc H Cl OAc OAc Cl H OAc ¹⁾ ¹⁾ H ¹⁾ Br H H Br ¹⁾ H ¹⁾ ¹⁾ H Br ¹⁾ HH ¹⁾ Br H ¹⁾ ¹⁾ H H Cl H H Cl H H H H H H Cl H H Cl H H ¹⁾ ¹⁾ H H Br H HBr H H H H H Br H H H H Br H OMe OMe OAc H Cl OAc OAc H Cl OAc H H H BrH H H H Br ¹⁾O(CH₂)₅Me,

The compounds of the formula XI are obtained by reacting a compound ofthe formula XIV with an alkine of formula R³—≡—R⁴:

The Diels-Alder reaction can be performed according to, or in analogy tomethods described in Klaus Müllen et al., J. Am. Chem. Soc 2004, 126,7794-7795 and Klaus Müllen et al., J. Am. Chem. Soc 2006, 128,1334-1339.

The compounds of formula XIV are new and form a further embodiment ofthe present invention. Accordingly, the present invention is alsodirected compounds of the formula

wherein X¹¹, Ar¹, Ar², n₁, n₂, R¹, R², R⁵, R⁶ and m are as definedabove, with the proviso that the following compound is excluded:

and with the further proviso that compounds of formula XIV are excluded,wherein R¹ and R² are a group of formula

wherein A is a coupling residue having phenolic OH, X¹¹ is halogen, n₁,n₂ and m are 0.

The compounds of the formula XIV can be synthesized via a “Knoevennagel”condensation:

(see, for example, Klaus Müllen et al., J. Am. Chem. Soc 2006, 128,1334-1339 and literature cited therein).

The alkines can be prepared via Sonogashira coupling (see, for example,Jason M. Nolan and Daniel L. Comins, J. Org. Chem. 2003, 68, 3736-3738;Zhaoguo Zhang et al., J. Org. Chem. 2004, 69, 5428-5432; Dmitri Gelman,Stephen L. Buchwald, Angew. Chem. Int. Ed. 2003, 42, 5993-5996; Rik R.Tykwinski, Angew. Chem. 2003, 115, 1604-1606).

In one embodiment, the polymers according to the invention consist onlyof one or more type of repeating units of formula I. In a preferredembodiment, the polymers according to the invention consist of preciselyone type of repeating unit of formula I (homopolymers).

According to the present invention the term “polymer” comprises polymersas well as oligomers, wherein a polymer is a molecule of high relativemolecular mass, the structure of which essentially comprises therepetition of units derived, actually or conceptually, from molecules oflow relative molecular mass and an oligomer is a molecule ofintermediate molecular mass, the structure of which essentiallycomprises a small plurality of units derived, actually or conceptually,from molecules of lower relative molecular mass. A molecule is regardedas having a high relative molecular mass if it has properties which donot vary significantly with the removal of one or a few of the units. Amolecule is regarded as having an intermediate molecular mass if it hasproperties which do vary significantly with the removal of one or a fewof the units.

According to the present invention a homopolymer is a polymer derivedfrom one species of (real, implicit, or hypothetical) monomer. Manypolymers are made by the mutual reaction of complementary monomers.These monomers can readily be visualized as reacting to give an“implicit monomer”, the homopolymerisation of which would give theactual product, which can be regarded as a homopolymer. Some polymersare obtained by chemical modification of other polymers, such that thestructure of the macromolecules that constitute the resulting polymercan be thought of having been formed by the homopolymerisation of ahypothetical monomer.

Accordingly a copolymer is a polymer derived from more than one speciesof monomer, e.g. bipolymer, terpolymer, quaterpolymer, etc.

The oligomers of this invention have a weight average molecular weightof <2,000 Daltons. The polymers of this invention preferably have aweight average molecular weight of 2,000 Daltons or greater, especially2,000 to 2,000,000 Daltons, more preferably 10,000 to 1,000,000 and mostpreferably 20,000 to 500,000 Daltons. Molecular weights are determinedaccording to gel permeation chromatography using polystyrene standards.

The present invention is illustrated in more detail on the basis of anespecially preferred embodiment below, but should not be limitedthereto. In said embodiment the polymer is a polymer of formula

whereinAr¹, n₁, Ar², n₂, R¹, R², R³, R⁴, R⁵, R⁶ and m are as defined above, Tand Ar³ are as defined in WO06/097419, wherein Ar³ can also be arepeating unit of formula

as described in WO06/097419, whereinR^(7′) is an organic substituent, wherein two or more substituentsR^(7′) in the same molecule may have different meanings, or can formtogether an aromatic, or heteroaromatic ring, or ring system, andX′ is 0, or an integer of 1 to 5.A is a 5-, 6-, or 7-membered heteroaromatic ring, containing oneheteroatom selected from nitrogen, oxygen and sulphur, which can besubstituted and/or can be part of a fused aromatic or heteroaromaticring system,R^(1′) and R^(4′) are hydrogen,R^(2′), R^(3′) R^(5′) and R^(6′) are independently of each other H,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is interrupted by D,C₁-C₁₈perfluoroalkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is interrupted byD, C₇-C₂₅aralkyl, or a group —X²—R^(18′),R^(8′) and R^(9′) are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is interrupted by D, C₁-C₁₈perfluoroalkyl,C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is interrupted by D, or a group—X²—R^(18′), or two substituents R^(2′) and R^(3′) and/or R^(5′) andR^(6′), which are adjacent to each other, together form a group

or two substituents R^(5′) and R^(3′), which are adjacent to each other,together form a group

orR⁸ and R⁹ together form a group

wherein R^(205′), R^(206′), R^(207′), R^(208′)R^(209′) and R^(210′) areindependently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₁-C₁₈alkoxy, or C₁-C₁₈alkoxywhich is substituted by E and/or interrupted by D, C₁-C₁₈perfluoroalkyl,R^(10′) is H, C₆-C₁₈aryl, which can be substituted by G,C₂-C₁₈heteroaryl, which can be substituted by G, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is interrupted by D, C₁-C₁₈perfluoroalkyl,C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interruptedby D, or a group —X²—R^(18′), wherein X² is a spacer, such asC₆-C₁₂aryl, or C₆-C₁₂heteroaryl, especially phenyl, or naphthyl, whichcan be substituted one more, especially one to two times withC₁-C₁₈alkyl, C₁-C₁₈alkyl which is interrupted by D,C₁-C₁₈perfluoroalkyl, C₁-C₁₈alkoxy, or C₁-C₁₈alkoxy which is substitutedby E and/or interrupted by D, and R^(18′) is H, C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is interrupted by D, C₁-C₁₈perfluoroalkyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is interrupted by D, or —NR^(25′) R^(26′);

X′ is O, S, or NR^(17′),

R^(11′) and R^(14′) are hydrogen,R^(12′), R^(13′), R^(15′) and R^(16′) are hydrogen,R^(17′) is C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl,C₁-C₁₈perfluoroalkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl whichis interrupted by —O—; ortwo substituents R^(11′) and R^(12′), and/or R^(14′) and R^(16′),R^(12′) and R^(13′) and/or R^(15′) and R^(16′), which are adjacent toeach other, together form a group

or two substituents R^(15′) and R^(13′), which are adjacent to eachother, together form a group

wherein R^(105′) R^(106′), R^(107′) and R^(108′) are independently ofeach other H, or C₁-C₈alkyl, D, E and G are as defined above;a is 1,b is 0, or 1,c is 0.005 to 1,d is 0, or 1,e is 0, or 1, wherein e is not 1, if d is 0,f is 0.995 to 0, wherein the sum of c and f is 1.

Ar³ is preferably selected from repeating units of formula:

whereinR⁴⁴ and R⁴¹ are hydrogen, C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, andR⁴⁵ is H, C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, especially C₁-C₁₈alkyl which is interrupted by —O—,R¹¹⁶ and R¹¹⁷ are independently of each other H, halogen, —CN,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, C₇-C₂₅aralkyl, —C(═O)—R¹²⁷, —C(═O)OR¹²⁷, or—C(═O)NR¹²⁷R¹²⁶,R¹¹⁹ and R¹²⁰ are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, or C₇-C₂₅aralkyl, or R¹¹⁹ and R¹²⁰ togetherform a group of formula ═CR¹²¹R¹²², whereinR¹²¹ and R¹²² are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂-C₂₀heteroaryl,or C₂-C₂₀heteroaryl which is substituted by G, orR¹¹⁹ and R¹²⁰ together form a five or six membered ring, whichoptionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D,C₇-C₂₅aralkyl, or —C(═O)—R¹²⁷, andR¹²⁶ and R¹²⁷ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—, wherein G, D and E are asdefined above.

The repeating units T are in particular selected from the followinggroup VI:

whereinX¹ is a hydrogen atom, or a cyano group,R¹¹⁶ and R¹¹⁷ are as defined above,R⁴¹ can be the same or different at each occurrence and is Cl, F, CN,N(R⁴⁵)₂, a C₁-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, a C₁-C₂₅alkoxygroup, in which one or more carbon atoms which are not in neighbourhoodto each other could be replaced by —NR⁴⁵—, —O—, —S—, —C(═O)—O—, or—O—C(═O)—O—, and/or wherein one or more hydrogen atoms can be replacedby F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein one or morecarbon atoms can be replaced by O, S, or N, and/or which can besubstituted by one or more non-aromatic groups R⁴¹, or two or moregroups R⁴¹ form a ring system;R⁴⁵ is H, a C₁-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, in which one ormore carbon atoms which are not in neighbourhood to each other could bereplaced by —NR^(45′)—, —O—, —S—, —C(═O)—O—, or, —O—C(═O)—O—, and/orwherein one or more hydrogen atoms can be replaced by F, a C₆-C₂₄arylgroup, or a C₆-C₂₄aryloxy group, wherein one or more carbon atoms can bereplaced by O, S, or N, and/or which can be substituted by one or morenon-aromatic groups R⁴¹,R^(45′) is H, a C₁-C₂₅alkyl group, or a C₄-C₁₈cycloalkyl group,n can be the same or different at each occurrence and is 0, 1, 2, or 3,especially 0, 1, or 2, very especially 0 or 1, and u is 1, 2, 3, or 4;A⁴ is a C₆-C₂₄aryl group, a C₂-C₃₀heteroaryl group, especially phenyl,naphthyl, anthryl, biphenylyl, 2-fluorenyl, phenanthryl, or perylenyl,which can be substituted by one or more non-aromatic groups R⁴¹, whereinT is preferably a repeating unit of formula VIa, VIb or VIf.Homopolymers of formula VII, wherein a=1, b=0, c=1, d=0, e=0, f=0, are,for example, obtained by nickel coupling reactions, especially theYamamoto reaction:

wherein Ar¹, n₁, Ar², n₂, R¹, R², R³, R⁴, R⁵, R⁶ and m are as definedabove. In said aspect homopolymers consisting of repeating units offormula IIIa are preferred and homopolymers consisting of repeatingunits of formula IIa are most preferred.

Copolymers of formula VII, involving repeating units of formula I and—Ar³— (a=1, c=0.995 to 0.005, b=0, d=1, e=0, f=0.005 to 0.995), can beobtained by nickel coupling reactions:

wherein X¹⁰ is a repeating unit of formula I, especially II and III,very especially IIa and IIIa, c, f and Ar³ are as defined above.

Polymerization processes involving only dihalo-functional reactants maybe carried out using nickel coupling reactions. One such couplingreaction was described by Colon et al. in J. Pol. Sci., Part A, PolymerChemistry Edition 28 (1990) 367, and by Colon et al. in J. Org. Chem. 51(1986) 2627. The reaction is typically conducted in a polar aproticsolvent (e.g., dimethylacetamide) with a catalytic amount of nickelsalt, a substantial amount of triphenylphosphine and a large excess ofzinc dust. A variant of this process is described by loyda et al. inBull. Chem. Soc. Jpn, 63 (1990) 80 wherein an organo-soluble iodide wasused as an accelerator.

Another nickel-coupling reaction was disclosed by Yamamoto in Progressin Polymer Science 17 (1992) 1153 wherein a mixture of dihaloaromaticcompounds was treated with an excess amount of nickel(1,5-cyclooctadiene) complex in an inert solvent. All nickel-couplingreactions when applied to reactant mixtures of two or more aromaticdihalides yield essentially random copolymers. Such polymerizationreactions may be terminated by the addition of small amounts of water tothe polymerization reaction mixture, which will replace the terminalhalogen groups with hydrogen groups. Alternatively, a monofunctionalaryl halide may be used as a chain-terminator in such reactions, whichwill result in the formation of a terminal aryl group.

Nickel-coupling polymerizations yield essentially homopolymers or randomcopolymers comprising units of formula I and units derived from otherco-monomers.

Homopolymers of formula VII, wherein a=1, c=1, b=0, d=1, e=0, f=1, canbe obtained, for example, by the Suzuki reaction:

wherein X¹⁰ and Ar³ are as defined above.

The condensation reaction of an aromatic boronate and a halogenide,especially a bromide, commonly referred to as the “Suzuki reaction”, istolerant of the presence of a variety of organic functional groups asreported by N. Miyaua and A. Suzuki in Chemical Reviews, Vol. 95, pp.457-2483 (1995). This reaction can be applied to preparing highmolecular weight polymers and copolymers. Preferred catalysts are2-dicyclohexylphosphino-2′,6′-di-alkoxybiphenyl/palladium(II) acetates.An especially preferred catalyst is2-dicyclohexylphosphino-2′,6′-di-methoxybiphenyl(sPhos)/palladium(II)acetate.

To prepare polymers corresponding to formula VIIc, a dihalogenide, suchas a dibromide or dichloride, especially a dibromide corresponding toformula Br—X¹⁰—Br is reacted with an equimolar amount of a diboronicacid or diboronate corresponding to formula

wherein X¹¹ is independently in each occurrence —B(OH)₂, —B(OY¹¹)₂ or

wherein Y¹¹ is independently in each occurrence a C₁-C₁₀alkyl group andY¹² is independently in each occurrence a C₂-C₁₀alkylene group, such as—CY¹³Y¹⁴—CY¹⁵Y¹⁶—, or —CY¹⁷Y¹⁸—CY¹⁹Y²⁰—CY²¹Y²²—, wherein Y¹³, Y¹⁴, Y¹⁵,Y¹⁶, Y¹⁷, Y¹⁸, Y¹⁹, Y²⁰, Y²¹ and Y²² are independently of each otherhydrogen, or a C₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, or—C(CH₃)₂CH₂C(CH₃)₂—, under the catalytic action of Pd and a phosphineligand, especially triphenylphosphine. The reaction is typicallyconducted at about 70° C. to 180° C. in an aromatic hydrocarbon solventsuch as toluene. Other solvents such as dimethylformamide andtetrahydrofuran can also be used alone, or in mixtures with an aromatichydrocarbon. An aqueous base, preferably sodium carbonate, potassiumcarbonate, K₃PO₄, or bicarbonate, is used as the HBr scavenger.Depending on the reactivities of the reactants, a polymerizationreaction may take 2 to 100 hours. Organic bases, such as, for example,tetraalkylammonium hydroxide, and phase transfer catalysts, such as, forexample TBAB, can promote the activity of the boron (see, for example,Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 andreferences cited therein). Other variations of reaction conditions aregiven by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994)5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol. RapidCommun. 17 (1996) 239-252.

If desired, a monofunctional aryl halide or aryl boronate may be used asa chain-terminator in such reactions, which will result in the formationof a terminal aryl group.

It is possible to control the sequencing of the monomeric units in theresulting copolymer by controlling the order and composition of monomerfeeds in the Suzuki reaction.

Homopolymers of formula VII, wherein a=1, c=1, b=1, d=0, e=0, f=0, canbe obtained, for example by the Heck reaction:

wherein X¹⁰ and T are as defined above.

Polyphenylenethenylene derivatives and polyphenylenethynylenederivatives can be obtained by polymerization of divinyl or diethinylcompounds with dihalogen compounds by the Heck reaction (R. F. Heck,Palladium Reagents in Organic Synthesis, Academic Press, New York 1985,pp. 179; L. S. Hegedus, Organometalics in Synthesis, Ed. M. Schlosser,Wiley, Chichester, UK 1994, pp. 383; Z. Bao, Y. Chen, R. Cai, L. Yu,Macromolecules 26 (1993) pp. 5281; W.-K. Chan, L. Yu, Macromolecules 28(1995) pp. 6410; A. Hilberer, H.-J. Brouwer, B.-J. van der Scheer, J.Wildeman, G. Hadziioannou, Macromolecules 1995, 28, 4525) and theSonogaschira reaction (Dmitri Gelman and Stephen L. Buchwald, Angew.Chem. Int. Ed. 42 (2003) 5993-5996; Rik R. Tykwinski, Angew. Chem. 115(2003) 1604-1606; Jason M. Nolan and Daniel L. Comins, J. Org. Chem. 68(2003) 3736-3738; Jiang Cheng et al., J. Org. Chem. 69 (2004) 5428-5432;Zolta'n Nova'k et al., Tetrahedron 59 (2003) 7509-7513):

(Random) copolymers of formula VII, wherein a is 1, b is 1, c is 0.005to 0.995, d is 1, e is 1, f is 0.995 to 0.005, wherein the sum of c andf is 1, can also be obtained by the Heck reaction:

wherein a, b, c, d, e, f, X¹⁰, Ar³ and T are as defined above.

The polymers containing groups of formulas (I) may be prepared by anysuitable process, but are preferably prepared by the processes describedabove.

The polymers of the present invention can optionally comprise endmoieties E¹, wherein E¹ is an aryl moiety which may optionally besubstituted with a reactive group capable of undergoing chain extensionor crosslinking, or a tri(C₁-C₁₈)alkylsiloxy group. As used herein, areactive group capable of undergoing chain extension or crosslinkingrefers to any group which is capable of reacting with another of thesame group or another group so as to form a link to prepare polymers.Preferably, such reactive group is a hydroxy, glycidyl ether, acrylateester, methacrylate ester, ethenyl, ethynyl, maleimide, naphthimide,oxetane, trifluorovinyl ether moiety or a cyclobutene moiety fused tothe aromatic ring of E¹.

The polymers of the present invention, where E¹ are reactive groups asdefined above, are capable of crosslinking to form solvent resistant,heat-resistant films at 100° C. or more, more preferably at 150° C. ormore. Preferably, such crosslinking occurs at 350° C. or less, morepreferably 300° C. or less and most preferably 250° C. or less. Thecrosslinkable polymers of the invention are stable at 100° C. or moreand more preferably 150° C. or more. “Stable” as used herein means thatsuch polymers do not undergo crosslinking or polymerization reactions ator below the stated temperatures. If a crosslinkable material isdesired, E¹ is preferably a vinylphenyl, an ethynylphenyl, or 4-(or3-)benzocyclobutenyl radical. In another embodiment, E¹ is selected froma group of phenolic derivatives of the formula —C₆H₄—O—Y, wherein Y is—H, —CN,

If desired, the cross-linkable groups can be present in other parts ofthe polymer chain. For example, one of the substituents of theco-monomer T may be a crosslinkable group E¹.

The end-capping agent E¹-X¹² (E¹ is as defined above and X¹² is eitherCl or Br) is incorporated into the polymers of the present inventionunder the condition in which the resulting polymers are substantiallycapped by the reactive group E¹. The reactions useful for this purposeare the nickel-coupling, Heck reactions and Suzuki reactions describedabove. The average degree of polymerization is controlled by the moleratio of monomers to end-capping agent.

The polymers according to the invention can be worked up by knownmethods which are familiar to the person skilled in the art, asdescribed, for example, in D. Braun, H. Cherdron, H. Ritter, Praktikumder makromolekularen Stoffe, 1^(st) Edn., Wiley VCH, Weinheim 1999, p.68-79 or R. J. Young, P. A. Lovell, Introduction to Polymers, Chapman &Hall, London 1991. For example, the reaction mixture can be filtered,diluted with aqueous acid, extracted and the crude product obtainedafter drying and stripping-off of the solvent can be further purified byreprecipitation from suitable solvents with addition of precipitants.Residual palladium can be removed by using activated carbon,chromatography etc. Advantageously, the residual palladium could bereduced to <3 ppm by washing the crude organic solvent layer containingthe polymer with an aqueous solution of L-cysteine at room temperatureto the boiling point of the organic solvent, especially by washing atoluene layer containing the polymer with an aqueous solution ofL-cysteine at 85 to 90° C., optionally followed by washing with asolution of L-cysteine and sodium thiosulfate at 78 to 82° C. (MahavirPrashad, Yugang Liu, Oljan Repicoe, Adv. Synth. Catal. 2003, 345,533-536; Christine E. Garrett, Kapa Prasad, Adv. Synth. Catal. 2004,346, 889-900). Additionally the Pd can be removed by washing the polymerwith an aqueous NaCN solution as described in U.S. Pat. No. 6,956,095.Polymer-analogous reactions can subsequently be carried out for furtherfunctionalization of the polymer. Thus, for example, terminal halogenatoms can be removed reductively by reduction with, for example, LiAlH₄(see, for example, J. March, Advanced Organic Chemistry, 3^(rd) Edn.McGraw-Hill, p. 510).

Another aspect of this invention is related to polymer blends containing1 to 99 percent of at least one containing polymers comprising a unit offormula I. The remainder 1 to 99 percent of the blend is composed of oneor more polymeric materials selected from among chain growth polymerssuch as polystyrene, polybutadiene, poly(methyl methacrylate), andpoly(ethylene oxide); step-growth polymers such as phenoxy resins,polycarbonates, polyamides, polyesters, polyurethanes, and polyimides;and crosslinked polymers such as crosslinked epoxy resins, crosslinkedphenolic resins, crosslinked acrylate resins, and crosslinked urethaneresins. Examples of these polymers may be found in Preparative Methodsof Polymer Chemistry, W. R. Sorenson and T. W. Campbell, Second Edition,Interscience Publishers (1968). Also may be used in the blends areconjugated polymers such as poly(phenylene vinylene), substitutedpoly(phenylene vinylene)s, substituted polyphenylenes andpolythiophenes. Examples of these conjugated polymers are given byGreenham and Friend in Solid State Physics, Vol. 49, pp. 1-149 (1995).

In a preferred embodiment the present invention is directed to polymersof formula

wherein R³, R⁴, R⁵ and R⁶ are independently of each other H,C₁-C₂₅alkyl, which can optionally be interrupted by O, or C₁-C₂₅alkoxy,which can optionally be interrupted by O,R⁴⁴ and R^(44′) are independently of each other H, C₁-C₂₅alkyl, whichcan optionally be interrupted by O, or C₁-C₂₅alkoxy, which canoptionally be interrupted by O, and n1 and n2 are independently of eachother 1, 2, or 3.

In an especially preferred embodiment the present invention is directedto polymers of formula

wherein R¹, R², R³ and R⁴ are independently of each other

wherein n₃ is 0, or an integer 1, 2, or 3, especially 0, or 1; and R¹¹can be the same or different and is H, C₁-C₂₅alkyl, which can beoptionally interrupted by O, or C₁-C₂₅alkoxy, which can be optionallyinterrupted by O, and

Ar³′ is

whereinR⁴⁴, R¹¹⁶, R¹¹⁷, R¹¹⁹ and R¹²⁰ are as defined above,R^(8′) and R^(9′) are independently of each other

wherein n₃ and R¹¹ are as defined above, R^(17′) is C₁-C₂₅alkyl, whichcan be optionally interrupted by O, and

R^(10′) is R^(8′), or

wherein n2 is 0, 1, or 2.

The following polymers are especially preferred:

The polymers of the present invention can show high photoluminescenceand/or electroluminescence.

Halogen is fluorine, chlorine, bromine and iodine.

C₁-C₂₅alkyl is typically linear or branched, where possible. Examplesare methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl,tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl,1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl,1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl.C₁-C₈alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl,sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl. C₁-C₄alkyl is typicallymethyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl,tert.-butyl.

C₁-C₂₅alkoxy groups are straight-chain or branched alkoxy groups, e.g.methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy,isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy,pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy. Examples ofC₁-C₈alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec.-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, 2-pentyloxy,3-pentyloxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy,1,1,3,3-tetramethylbutoxy and 2-ethylhexyloxy, preferably C₁-C₄alkoxysuch as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec.-butoxy, isobutoxy, tert.-butoxy. The term “alkylthio group” meansthe same groups as the alkoxy groups, except that the oxygen atom of theether linkage is replaced by a sulfur atom.

C₂-C₂₅alkenyl groups are straight-chain or branched alkenyl groups, suchas e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl,isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl,n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.

C₂₋₂₄alkynyl is straight-chain or branched and preferably C₂₋₈alkynyl,which may be unsubstituted or substituted, such as, for example,ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl,2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl,1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl,trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl,1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.

C₁-C₁₈perfluoroalkyl, especially C₁-C₄perfluoroalkyl, is a branched orunbranched radical such as for example —CF₃, —CF₂CF₃, —CF₂CF₂CF₃,—CF(CF₃)₂, —(CF₂)₃CF₃, and —C(CF₃)₃.

The terms “haloalkyl, haloalkenyl and haloalkynyl” mean groups given bypartially or wholly substituting the above-mentioned alkyl group,alkenyl group and alkynyl group with halogen, such as trifluoromethyletc. The “aldehyde group, ketone group, ester group, carbamoyl group andamino group” include those substituted by an alkyl group, a cycloalkylgroup, an aryl group, an aralkyl group or a heterocyclic group, whereinthe alkyl group, the cycloalkyl group, the aryl group, the aralkyl groupand the heterocyclic group may be unsubstituted or substituted. The term“silyl group” means a group of formula —SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³and R⁶⁴ are independently of each other a C₁-C₈alkyl group, inparticular a C₁-C₄ alkyl group, a C₆-C₂₄aryl group or a C₇-C₁₂aralkylgroup, such as a trimethylsilyl group. The term “siloxanyl group” meansa group of formula —O—SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³ and R⁶⁴ are asdefined above, such as a trimethylsiloxanyl group.

The term “cycloalkyl group” is typically C₅-C₁₂cycloalkyl, such ascyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl,cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted orsubstituted. The term “cycloalkenyl group” means an unsaturatedalicyclic hydrocarbon group containing one or more double bonds, such ascyclopentenyl, cyclopentadienyl, cyclohexenyl and the like, which may beunsubstituted or substituted. The cycloalkyl group, in particular acyclohexyl group, can be condensed one or two times by phenyl which canbe substituted one to three times with C₁-C₄-alkyl, halogen and cyano.Examples of such condensed cyclohexyl groups are:

in particular

wherein R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵ and R⁵⁶ are independently of each otherC₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano, in particular hydrogen.

Aryl is usually C₆-C₃₀aryl, preferably C₆-C₂₄aryl, which optionally canbe substituted, such as, for example, phenyl, 4-methylphenyl,4-methoxyphenyl, naphthyl, especially 1-naphthyl, or 2-naphthyl,biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl,anthryl, tetracyl, pentacyl, hexacyl, or quaderphenylyl, which may beunsubstituted or substituted.

The term “aralkyl group” is typically C₇-C₂₄aralkyl, such as benzyl,2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl,ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl,ω-phenyl-eicosyl or ω-phenyl-docosyl, preferably C₇-C₁₈aralkyl such asbenzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl,ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl orω-phenyl-octadecyl, and particularly preferred C₇-C₁₂aralkyl such asbenzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl,ω-phenyl-butyl, or ω,ωdimethyl-phenyl-butyl, in which both the aliphatichydrocarbon group and aromatic hydrocarbon group may be unsubstituted orsubstituted.

The term “aryl ether group” is typically a C₆₋₂₄aryloxy group, that isto say O—C₆₋₂₄aryl, such as, for example, phenoxy or 4-methoxyphenyl.The term “aryl thioether group” is typically a C₆₋₂₄arylthio group, thatis to say S—C₆₋₂₄aryl, such as, for example, phenylthio or4-methoxyphenylthio. The term “carbamoyl group” is typically aC₁₋₁₈carbamoyl radical, preferably C₁₈carbamoyl radical, which may beunsubstituted or substituted, such as, for example, carbamoyl,methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl,dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

The terms “aryl” and “alkyl” in alkylamino groups, dialkylamino groups,alkylarylamino groups, arylamino groups and diarylgroups are typicallyC₁-C₂₅alkyl and C₆-C₂₄aryl, respectively.

Alkylaryl refers to alkyl-substituted aryl radicals, especiallyC₇-C₁₂alkylaryl. Examples are tolyl, such as 3-methyl-, or4-methylphenyl, or xylyl, such as 3,4-dimethylphenyl, or3,5-dimethylphenyl.

Heteroaryl is typically C₂-C₂₆heteroaryl, i.e. a ring with five to sevenring atoms or a condensed ring system, wherein nitrogen, oxygen orsulfur are the possible hetero atoms, and is typically an unsaturatedheterocyclic group with five to 30 atoms having at least six conjugatedπ-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl,thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl,isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl,pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl,pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl,quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl,chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl,carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl,pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl,isoxazolyl, furazanyl or phenoxazinyl, which can be unsubstituted orsubstituted.

Possible substituents of the above-mentioned groups are C₁-C₈alkyl, ahydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen,halo-C₁-C₈alkyl, a cyano group, an aldehyde group, a ketone group, acarboxyl group, an ester group, a carbamoyl group, an amino group, anitro group or a silyl group.

If a substituent, such as, for example R⁷ occurs more than one time in agroup, it can be different in each occurrence.

The wording “substituted by G” means that one, or more, especially oneto three substituents G might be present.

As described above, the aforementioned groups may be substituted by Eand/or, if desired, interrupted by D. Interruptions are of coursepossible only in the case of groups containing at least 2 carbon atomsconnected to one another by single bonds; C₆-C₁₈aryl is not interrupted;interrupted arylalkyl or alkylaryl contains the unit D in the alkylmoiety. C₁-C₁₈alkyl substituted by one or more E and/or interrupted byone or more units D is, for example, (CH₂CH₂O)₁₋₉—R^(x), where R^(x) isH or C₁-C₁₀alkyl or C₂-C₁₀alkanoyl (e.g. CO—CH(C₂H₅)C₄H₉),CH₂—CH(OR^(y′))—CH₂—O—R^(y), where R^(y) is C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl, phenyl, C₇-C₁₅phenylalkyl, and R^(y′) embraces thesame definitions as R^(y) or is H;

C₁-C₈alkylene-COO—R^(z), e.g. CH₂COOR_(z), CH(CH₃)COOR^(z),C(CH₃)₂COOR^(z), where R^(z) is H, C₁-C₁₈alkyl, (CH₂CH₂O)₁₋₉—R^(x), andR^(x) embraces the definitions indicated above; CH₂CH₂—O—CO—CH═CH₂;CH₂CH(OH)CH₂—O—CO—C(CH₃)═CH₂.

Preferred arylene radicals are 1,4-phenylene, 2,5-tolylene,1,4-naphthylene, 1,9 antracylene, 2,7-phenantrylene and2,7-dihydrophenantrylene.

Preferred heteroarylene radicals are 2,5-pyrazinylene,3,6-pyridazinylene, 2,5-pyridinylene, 2,5-pyrimidinylene,1,3,4-thiadiazol-2,5-ylene, 1,3-thiazol-2,4-ylene,1,3-thiazol-2,5-ylene, 2,4-thiophenylene, 2,5-thiophenylene,1,3-oxazol-2,4-ylene, 1,3-oxazol-2,5-ylene and1,3,4-oxadiazol-2,5-ylene, 2,5-indenylene and 2,6-indenylene.

Another aspect of the invention is the films formed from the polymers ofthe invention. Such films can be used in polymeric light-emitting diodes(PLEDs). Preferably, such films are used as emitting layers. These filmsmay also be used as protective coatings for electronic devices and asfluorescent coatings. The thickness of the coating or film is dependentupon the ultimate use. Generally, such thickness can be from 0.01 to 200microns. In that embodiment wherein the coating is used as a fluorescentcoating, the coating or film thickness is from 10 to 200 microns. Inthat embodiment where the coatings are used as electronic protectivelayers, the thickness of the coating can be from 5 to 20 microns. Inthat embodiment where the coatings are used in a polymericlight-emitting diode, the thickness of the layer formed is 0.01 to 0.5microns. The polymers of the invention form good pinhole- anddefect-free films. Such films can be prepared by means well known in theart including spin-coating, spray-coating, dip-coating androller-coating. Such coatings are prepared by a process comprisingapplying a composition to a substrate and exposing the appliedcomposition to conditions such that a film is formed. The conditionswhich form a film depend upon the application technique. Preferably, thesolution contains from 0.1 to 10 weight percent of the polymers. Thiscomposition is applied to the appropriate substrate by the desiredmethod and the solvent is allowed to evaporate. Residual solvent may beremoved by vacuum and/or by heat-drying. The films are preferablysubstantially uniform in thickness and substantially free of pinholes.In another embodiment, the polymers may be partially cured. This isknown as B-staging.

A further embodiment of the present invention is directed to anelectronic device or a component therefore, comprising a substrate and apolymer according to the present invention.

In such a device the polymers according to the present invention areused as electroluminescent material. For the purposes of the presentinvention, the term “electroluminescent material” is taken to meanmaterials which can be used as or in an active layer in anelectroluminescent device. The term “active layer” means that the layeris capable of emitting light (light-emitting layer) on application of anelectric field and/or that it improves the injection and/or transport ofthe positive and/or negative charges (charge injection or chargetransport layer). The invention therefore also relates to the use of thepolymers according to the invention as electroluminescent material. Theinvention furthermore relates to an electroluminescent material whichcomprises the polymers according to the invention. Electroluminescentdevices are used, for example, as self-illuminating display elements,such as control lamps, alphanumeric displays, signs and inopto-electronic couplers.

A device according to the present invention may be prepared inaccordance with the disclosure of WO99/48160, the contents of which areincorporated by reference. Polymers according to the present inventionmay be present in the device as the sole light emitting polymer or as acomponent in a blend further comprising hole and/or electrontransporting polymers. Alternatively, the device may comprise distinctlayers of a polymer of the present invention, a hole transportingpolymer and/or an electron transporting polymer.

In one embodiment the electronic device comprises an electroluminescentdevice, which comprises

(a) a charge injecting layer for injecting positive charge carriers,(b) a charge injecting layer for injecting negative charge carriers,(c) a light-emissive layer located between the layers (a) and (b)comprising a polymer according to the present invention.

The layer (a) may be a positive charge carrier transport layer which islocated between the light emissive layer (c) and an anode electrodelayer, or may be an anode electrode layer. The layer (b) may be anegative charge carrier transport layer which is located between thelight emissive layer (c) and an cathode electrode layer, or may be ancathode electrode layer. Optionally, an organic charge transport layercan be located between the light emissive layer (c) and one of thecharge carrier injecting layers (a) and (b).

The EL device emits light in the visible electromagnetic spectrumbetween 400 nm and 780 nm, preferably between 430 nm and 470 nm for ablue color, preferably between 520 nm and 560 nm for a green color,preferably between 600 nm and 650 nm for a red color. By incorporatingspecific repeating units in the backbone of the polymer the emission canbe even shifted to the near infrared (NIR, >780 nm).

It will be appreciated that the light emissive layer may be formed froma blend or mixture of materials including one or more polymers accordingto the present invention, and optionally further different polymers. Thefurther different polymers may be so-called hole transport polymers(i.e. to improve the efficiency of hole transport to the light-emissivematerial) or electron-transport polymers (i.e. to improve the efficiencyof electron transport to the light-emissive material). Preferably, theblend or mixture would comprise at least 0.1% by weight of a polymeraccording to the present invention, preferably at least 0.5% by weight,more preferably at least 1% by weight.

An organic EL device typically consists of an organic film sandwichedbetween an anode and a cathode such that when a positive bias is appliedto the device, holes are injected into the organic film from the anode,and electrons are injected into the organic film from the cathode. Thecombination of a hole and an electron may give rise to an exciton, whichmay undergo radiative decay to the ground state by liberating a photon.In practice the anode is commonly an mixed oxide of tin and indium forits conductivity and transparency. The mixed oxide (ITO) is deposited ona transparent substrate such as glass or plastic so that the lightemitted by the organic film may be observed. The organic film may be thecomposite of several individual layers each designed for a distinctfunction. Since holes are injected from the anode, the layer next to theanode needs to have the functionality of transporting holes. Similarly,the layer next to the cathode needs to have the functionality oftransporting electrons. In many instances, the hole-(electron)transporting layer also acts as the emitting layer. In some instancesone layer can perform the combined functions of hole and electrontransport and light emission. The individual layers of the organic filmmay be all polymeric in nature or combinations of films of polymers andfilms of small molecules deposited by thermal evaporation. It ispreferred that the total thickness of the organic film be less than 1000nanometers (nm). It is more preferred that the total thickness be lessthan 500 nm. It is most preferred that the total thickness be less than300 nm. It is preferred that the thickness of the active (lightemitting) layer be less than 400 nanometers (nm). It is more preferredthat the thickness is in the range of from 40 to 160 nm.

The ITO-glass, which serves as the substrate and the anode, may be usedfor coating after the usual cleaning with detergent, organic solventsand UV-ozone treatment. It may also be first coated with a thin layer ofa conducting substance to facilitate hole injection. Such substancesinclude copper phthalocyanine, polyaniline (PANI) andpoly(3,4-ethylenedioxy-thiophene) (PEDOT); the last two in their (doped)conductive forms, doped, for example, with FeCl₃ or Na₂S₂O₈. Theycontain poly(styrenesulfonic acid) (PSS) as counter-ion to ensure watersolubility. It is preferred that the thickness of this layer be 200 nmor less; it is more preferred that the thickness be 100 nm or less.

In the cases where a hole-transporting layer is used, the polymericarylamines described in U.S. Pat. No. 5,728,801, may be used. Otherknown hole-conducting polymers, such as polyvinylcarbazole, may also beused. The resistance of this layer to erosion by the solution of thecopolymer film which is to be applied next is obviously critical to thesuccessful fabrication of multi-layer devices. The thickness of thislayer may be 500 nm or less, preferably 300 nm or less, most preferably150 nm or less.

In the case where an electron-transporting layer is used, it may beapplied either by thermal evaporation of low molecular weight materialsor by solution coating of a polymer with a solvent that would not causesignificant damage to the underlying film.

Examples of low molecular weight materials include the metal complexesof 8-hydroxyquinoline (as described by Burrows et al. in Appl. Phys.Lett. 64 (1994) 2718-2720), metallic complexes of10-hydroxybenzoquinoline (as described by Hamada et al. in Chem. Lett.(1993) 906-906), 1,3,4-oxadiazoles (as described by Hamada et al. inOptoelectronics-Devices and Technologies 7 (1992) 83-93),1,3,4-triazoles (as described by Kido et al. in Chem. Lett. (1996)47-48), and dicarboximides of perylene (as described by Yoshida et al.in Appl. Phys. Lett. 69 (1996) 734-736).

Polymeric electron-transporting materials are exemplified by1,3,4-oxadiazole-containing polymers (as described by Li et al. in J.Chem. Soc. (1995) 2211-2212, by Yang and Pei in J. Appl. Phys. 77 (1995)4807-4809), 1,3,4-triazole-containing polymers (as described by Strukeljet al. in Science 267 (1995) 1969-1972), quinoxaline-containing polymers(as described by Yamamoto et al. in Jpn. J. Appl. Phys. 33 (1994)L250-L253, O'Brien et al. in Synth. Met. 76 (1996) 105-108), andcyano-PPV (as described by Weaver et al. in Thin Solid Films 273 (1996)39-47). The thickness of this layer may be 500 nm or less, preferably300 nm or less, most preferably 150 nm or less.

The cathode material may be deposited either by thermal evaporation orby sputtering. The thickness of the cathode may be from 1 nm to 10,000nm, preferably 5 nm to 500 nm.

OLEDs made according to the present invention may include phosphorescentdopants dispersed in the device's emissive layer, capable of achievinginternal quantum efficiencies approaching 100%. As used herein, the term“phosphorescence refers to emission from a triplet excited state of anorganic or metal-organic molecule. High efficiency organic lightemitting devices using phosphorescent dopants have been demonstratedusing several different conducting host materials (M. A. Baldo et al.,Nature, Vol 395, 151 (1998), C. Adachi et al., Appl. Phys. Lett., Vol.77, 904 (2000)).

In a preferred embodiment, the electroluminescent device comprises atleast one hole-transporting polymer film and a light-emitting polymerfilm comprised of the polymer of the invention, arranged between ananode material and a cathode material such that under an appliedvoltage, holes are injected from the anode material into thehole-transporting polymer film and electrons are injected from thecathode material into the light-emitting polymer films when the deviceis forward biased, resulting in light emission from the light-emittinglayer.

In another preferred embodiment, layers of hole-transporting polymersare arranged so that the layer closest to the anode has the loweroxidation potential, with the adjacent layers having progressivelyhigher oxidation potentials. By these methods, electroluminescentdevices having relatively high light output per unit voltage may beprepared.

The term “hole-transporting polymer film” as used herein refers to alayer of a film of a polymer which when disposed between two electrodesto which a field is applied and holes are injected from the anode,permits adequate transport of holes into the emitting polymer.Hole-transporting polymers typically are comprised of triarylaminemoieties. The term “light-emitting polymer film” as used herein refersto a layer of a film of a polymer whose excited states can relax to theground state by emitting photons, preferably corresponding towavelengths in the visible range. The term “anode material” as usedherein refers to a semi-transparent, or transparent, conducting filmwith a work function between 4.5 electron volts (eV) and 5.5 eV.Examples are gold, silver, copper, aluminum, indium, iron, zinc, tin,chromium, titanium, vanadium, cobalt, nickel, lead, manganese, tungstenand the like, metallic alloys such as magnesium/copper,magnesium/silver, magnesium/aluminum, aluminum/indium and the like,semiconductors such as Si, Ge, GaAs and the like, metallic oxides suchas indium-tin-oxide (“ITO”), ZnO and the like, metallic compounds suchas CuI and the like, and furthermore, electroconducting polymers suchpolyacetylene, polyaniline, polythiophene, polypyrrole,polyparaphenylene and the like. Oxides and mixed oxides of indium andtin, and gold are preferred. Most preferred is ITO, especially ITO onglass, or on a plastics material, such as polyester, for examplepolyethylene terephthalate (PET), as substrate.

The term “cathode material” as used herein refers to a conducting filmwith a work function between 2.0 eV and 4.5 eV. Examples are alkalimetals, earth alkaline metals, group 13 elements, silver, and copper aswell as alloys or mixtures thereof such as sodium, lithium, potassium,calcium, lithium fluoride (LiF), sodium-potassium alloy, magnesium,barium, magnesium-silver alloy, magnesium-copper alloy,magnesium-aluminum alloy, magnesium-indium alloy, aluminum,aluminum-aluminum oxide alloy, aluminum-lithium alloy, indium, calcium,and materials exemplified in EP-A 499,011, such as electroconductingpolymers e.g. polypyrrole, polythiophene, polyaniline, polyacetyleneetc. Preferably lithium, barium, calcium, magnesium, indium, silver,aluminum, or blends and alloys of the above are used. In the case ofusing a metal or a metallic alloy as a material for an electrode, theelectrode can be formed also by the vacuum deposition method. In thecase of using a metal or a metallic alloy as a material forming anelectrode, the electrode can be formed, furthermore, by the chemicalplating method (see for example, Handbook of Electrochemistry, pp383-387, Mazuren, 1985). In the case of using an electroconductingpolymer, an electrode can be made by forming it into a film by means ofanodic oxidation polymerization method onto a substrate, which ispreviously provided with an electroconducting coating.

As methods for forming said thin films, there are, for example, thevacuum deposition method, the spin-coating method, the casting method,the Langmuir-Blodgett (“LB”) method, the ink jet printing method and thelike. Among these methods, the vacuum deposition method, thespin-coating method, the ink jet printing method and the casting methodare particularly preferred in view of ease of operation and cost.

In the case of forming the layers by using the spin-coating method, thecasting method and ink jet printing method, the coating can be carriedout using a solution prepared by dissolving the composition in aconcentration of from 0.0001 to 90% by weight in an appropriate organicsolvent such as benzene, toluene, xylene, tetrahydrofurane,methyltetrahydrofurane, N,N-dimethylformamide, acetone, acetonitrile,anisole, dichloromethane, dimethylsulfoxide and mixtures thereof.

Patterning of active matrix OLED (AMOLED) materials for large format,high resolution displays can be done using Laser Induced Thermal Imaging(LITI; Organic Light-Emitting Materials and Devices VII, edited by ZakyaH. Kafafi, Paul A. Lane, Proceedings of SPIE Vol. 5519, 12-23).

The organic EL device of the present invention is seen as a futurereplacement technology for a flat panel display of an on-wall televisionset, a flat light-emitting device, such as a wall paper, a light sourcefor a copying machine or a printer, a light source for a liquid crystaldisplay or counter, a display signboard and a signal light and perhapseven to replace incandescent and fluorescent lamps. The polymers andcompositions of the present invention can be used in the fields of anorganic EL device, a photovoltaic device, an electrophotographicphotoreceptor, a photoelectric converter, a solar cell, an image sensor,and the like.

Accordingly, the present invention relates also to PLEDs, organicintegrated circuits (O—ICs), organic field effect transistors (OFETs),organic thin film transistors (OTFTs), organic solar cells (O—SCs),thermoelectric devices, or organic laser diodes comprising one or moreof the polymers according to the present invention.

The following examples are included for illustrative purposes only anddo not limit the scope of the claims. Unless otherwise stated, all partsand percentages are by weight. Weight-average molecular weight (M_(w))and polydispersity (M_(w)/M_(n)=PD) are determined by Gel PermeationChromatography (GPC) [Apparatus: GPC_(max)+TDA 302 from Viscotek(Houston, Tex., USA) yielding the responses form refractive index (RI),low angle light scattering (LALS), right angle light scattering (RALS)and differential viscosity (DP) measurements. Chromatographicconditions: Column: PL_(gel) mixed C (300×7.5 mm, 5 μm particles)covering the molecular weight range from about 1×10³ to about 2.5×10⁶ Dafrom Polymer Laboratories (Church Stretton, UK); Mobile phase:tetrahydrofuran containing 5 g/l of sodium trifluoroacetate; Mobilephase flow: either 0.5 or 0.7 ml/min; Solute concentration: about 1-2mg/ml; Injection volume: 100 μl; Detection: RI, LALS, RALS, DP.Procedure of molecular weight calibration: Relative calibration is doneby use of a set of 10 polystyrene calibration standards obtained fromPolymer Laboratories (Church Stretton, UK) spanning the molecular weightrange from 1,930,000 Da-5,050 Da, i.e., PS 1,930,000, PS 1,460,000, PS1,075,000, PS 560,000, PS 330,000, PS 96,000, PS 52,000, PS 30,300, PS10,100, PS 5,050 Da. Absolute calibration is done on the base of theresponses of LALS, RALS and DP. As experienced in a large number ofinvestigations this combination provides optimum calculation ofmolecular weight data. Usually PS 96,000 is used as the molecular weightcalibration standard, but in general every other PS standard lying inthe molecular weight range to be determined can be chosen for thispurpose.

All polymer structures given in the examples below are idealizedrepresentations of the polymer products obtained via the polymerizationprocedures described. If more than two components are copolymerized witheach other sequences in the polymers can be either alternating or randomdepending on the polymerisation conditions.

EXAMPLES Example 1

a) A solution of 1.40 g potassium hydroxide in 5.6 ml methanol is addedto 9.15 g (25 mmol) of 2,7-dibromo-phenanthrene-9,10-dione and 5.78 g(27.5 mmol) of 1,3-diphenyl-propan-2-one in 300 ml methanol. Thereaction mixture is refluxed for 30 min and cooled to 25° C. The productis filtered off, washed with methanol and dried (yield: 11.5 g (85%)).

b) 1 ml biphenylether is added to 540 mg (1 mmol) of the product ofexample 1a and 200 mg (1.10 mmol) diphenylacetylene. The reactionmixture is heated under argon for 5 h at 250° C. The biphenyl ether isdistilled off. The product is purified by chromatography on silica gelwith toluene/cyclohexane (1/5) (yield: 310 mg (45%); melting point:289-292° C.).

Example 2

In a Schlenk tube, a solution of 83 mg of Ni(COD)₂ and 48 mg bipyridinein 5 ml of toluene is degassed for 15 min. 310 mg of the correspondingdibrominated monomer is added to this solution and then the mixture isheated to 80° C. and stirred vigorously overnight. The solution ispoured on 100 ml of a 1/1/1 methanol/HCl/acetone mixture and stirred for1 h. The precipitate is then filtrated, dissolved in CHCl₃ and stirredvigorously at 60° C. with an aqueous solution ofethylenediaminetetraacetic acid (EDTA) tetrasodium salt for oneadditional hour. The organic phase is washed with water, concentratedand precipitated in methanol. The residue is purified by soxhletextraction using methanol and hexane and the polymer is then extractedwith CHCl₃ to give 115 mg of red powder.

M_(w)=21000

Solubility ˜1% by weight in chloroform

Photophysical Properties:

UV of chloroform solution at 2 different temperatures and spin coatedfilm on glass substrate made from a chloroform solution:

Annealing Conditions UV/Vis-absorption Solution at 50° C. 460 nmSolution at RT 480 nm, 505 nm film 485 nm, 515 nm

The bathochromic shift of the band at 460 nm shows the appearance ofstrong aggregation behaviour.

Application Example 1 Field-Effect Transistors a) Experimental:

Bottom-gate thin-film transistor (TFT) structures with p-Si gate wereused for all experiments. A high-quality thermal SiO₂ layer served asgate-insulator of C_(i)=32.6 nF/cm² capacitance per unit area. Sourceand drain electrodes were patterned by photolithography directly on thegate-oxide (bottom-contact configuration). On each substrate 16transistors are present with Au source/drain electrodes definingchannels of different length. Prior to the deposition of the organicsemiconductor the SiO₂ surface was derivatized with hexamethyldisilazane(HMDS) or octadecyltrichlorosilane (OTS). The films are prepared eitherby spin casting or drop casting the polymer obtained in example 1 indifferent solvents. The transistor behaviour is measured on an automatedtester elaborated by CSEM, Transistor Prober TP-10.

b) Transistor Performance:

The thin-film transistors showed clear p-type transistor behavior. Froma linear fit to the square root of the saturated transfercharacteristics a field-effect mobility of 10⁻⁴ cm²/Vs could bedetermined. The transistors showed a threshold voltage of about 0 V to 4V. The transistors showed decent on/off current ratios of 10⁴.

Example 3

A solution of 752.2 mg (1.089 mmol) of the product of example 1b and700.0 mg (1.089 mmol)2,7-bis(4,4,5,5,-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorenein 5 ml 1,4-dioxane and 5 ml toluene is degassed. 2.4 mg (0.011 mmol)palladium acetate and 27 mg (0.065 mmol)2-dicyclohexylphosphino-2′,6′-di-methoxybiphenyl are added. The reactionmixture is degassed. A degassed solution of 1.32 g (5.45 mmol) potassiumphosphate tribasic monohydrate in 3 ml water is added. The reactionmixture is refluxed after the addition of 5 and 10 ml toluene for 3 hand 3.5 h, respectively. The 30 ml degassed toluene and 260 mg (1.63mmol) degassed bromobenzene are added. The reaction mixture is refluxedfor 15 h. 20 ml degassed toluene and 560 mg (2.50 mmol)4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane in 3 ml degassedtoluene are added. The reaction mixture is stirred for 3 h. 30 mltoluene are added and the reaction mixture is washed with 100 ml 1%sodium cyanide solution. The toluene is partly distilled off and theremaining solution is poured into methanol. The polymer is filtered offand is washed with methanol, water acetone and methanol. The polymer isdissolved in toluene and is stirred at 90° C. with a 100 ml 1% sodiumcyanide solution for 2 h. The organic phase is separated off and thetoluene is partly distilled off. The remaining solution is poured intomethanol and the polymer is filtered off. The polymer is washed withmethanol (yield: 0.89 g (89%)).

GPC (polystyrene standard): M_(w)=130 00, PD=5.4.

Example 4

a) To 10.0 g (60.2 mmol) (4-hydroxy-phenyl)-acetic acid methyl ester and12.8 g (66.2 mmol) 3-bromomethyl-heptane in 100 ml DMF 25.0 g (181 mmol)potassium carbonate is added under nitrogen. The reaction mixture isheated to 120° C. for 2 h. Additional 5.81 g (3.01 mmol)3-bromomethyl-heptane and 12.5 g (9.03 mmol) potassium carbonate areadded. The reaction mixture is heated to 120° C. for additional 5 h. Thesolids are filtered off, washed with diethyl ether, the organic phase iswashed with water and dried with magnesium sulfate. The solvent isremoved in vacuum (yield: 14.1 g (84%)).

b) To 1.20 g (5.01 mmol) magnesium in 10 ml water free diethyl ether6.68 g (5.43 mmol) 2-brom-propane in 10 ml diethyl ether are slowlyadded under nitrogen. After the 2-brom-propane has been added, thereaction mixture is refluxed for 30 min. To this reaction mixture 12.0 g(4.18 mmol) of the product of example 4a are added at 0° C. The reactionmixture is stirred for 3 h at 25° C., ice is added to the reactionmixture, the reaction mixture is acidified with sulfuric acid (96%) andstirred for 30 min. The reaction mixture is extracted with diethylether. The solvent is distilled off. 100 ml glacial acetic acid and 20ml 20% hydrochloric acid are added. The reaction mixture is refluxed for2.5 h. The formed oil is separated, diluted with diethyl ether andwashed with water. The organic phase is dried with magnesium sulfate.The solvent is distilled off (yield: 8.86 g (91%)).

c) To 8.42 g (18.0 mmol) of the product of example 4b and 5.50 g (15.0mmol) 2,7-dibromo-phenanthrene-9,10-dione in 200 ml methanol 840 mg(15.0 mmol) potassium hydroxide in 5 ml methanol are added under argon.The reaction mixture is refluxed for 3 h. The reaction mixture is cooledto 25° C. and the product is filtered off (yield: 8.26 g (70%)).

d) To 8.00 g (10.0 mmol) of the product of example 4c in 16 ml diphenylether 1.97 g (11.1 mmol) diphenyl-acetylene are added under argon. Thereaction mixture is heated to 250° C. (outside temperature) for 2.5 h.The diphenyl ether is distilled off. The crude product is dissolved incyclohexane and filtered on silica gel. The solvent is distilled off. Acolumn chromatography on silica gel with cyclohexane/ethyl acetate(40/1) leads to the desired product (yield: 2.61 g (27%)).

e) Example 3 is repeated, except that instead of the product of example3 the product of example 4d is used (GPC (polystyrene standard):M_(w)=39 000, PD=13.8).

Example 5

a) The product is prepared according to example 4b.

b) The product is prepared according to example 4c.

c) The product is prepared according to example 4d (melting point:302-308° C.).

Application Example 2

An organic luminescence device having a single organic layer is preparedin the following manner: On a glass substrate, a 100 nm thick ITO filmis formed by sputtering and subsequently patterned. Onto oxygen-plasmatreated ITO film a 80 nm thick hole-injection layer using PEDOT:PSS(Baytron P, Al4083, HC Starck) is formed by spin-coating followed byheating at 200° C. (5 minutes). A solution of 66 mg of the polymer ofexample 3 and 33 mg of2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD) in 10 gof toluene are applied by spin coating (2500 rpm; 10 sec) to obtain athickness of 80 nm. Afterwards the substrate is set in a vacuumdeposition chamber, a cathode having a two-layer electrode structure isformed by depositing 50 nm barium followed by 100 nm aluminium. When thedevice is driven at a current density of 10 mA/cm² the resulting currentefficiency was 1.07 cd/A at CIE of 0.21, 0.20.

Application Example 3

The device is prepared and evaluated in the same manner as described inapplication example 2, except for using the polymer of example 4e in ablend of 2/3 the emitter polymer and 1/3 of a well known holetransporting moleculeN,N′-diphenyl-N,N′-(bis(3-methylphenyl)-[1,1-bi-phenyl]-4,4′-diamine(TPD). The current efficiency was 0.18 cd/A at 6V with the colorcoordinates x=0.33, y=0.44.

Example 6

The Diels-Alder reaction between product of example 1a (378 mg, 0.7mmol) and 1 equivalent of 1-phenyl-1-nonyne (140 mg, 0.7 mmol) usingdiphenylether as a solvent at >259° C. affords the desired monomer6,11-dibromo-2-heptyl-1,3,4-triphenyl-triphenylene. The biphenyl isdestilled off and the product is separated on silica gel column withhexane yielding 250 mg (50% yield).

Example 7

1-(dodec-1-ynyl)-4-octylbenzene is obtained via Sonogashira couplingreaction between 1-dodecyne and 0.8 equivalent of1-bromo-4-octyl-benzene in the presence of the catalyst Pd(PPh₃)₄/CuIand the base piperidine at 50° C. gave 1-(dodec-1-ynyl)-4-octylbenzenein 70% yield. Subsequent Diels-Alder reaction between 990 mg (1.85 mmol)of product of example 1a and 656 mg (1.85 mmol) of1-(dodec-1-ynyl)-4-octylbenzene using diphenylether as solvent at >259°C. affords 880 mg (55% yield) of the product after column chromatographyfrom hexane.

Example 8

The microwave assisted Suzuki reaction is performed using 229.9 mg(0.265 mmol) monomer from example 7 with 1 equivalent ofbis(pinacolato)diboron (0.265 mmol, 87.56 mg) and the catalyst Pd(PPh₃)₄(0.013266 mmol, 15.329 mg) together with 2 ml of K₂CO₃ (2M/H₂O solution)in toluene at 100° C. for 1 h (50W & 7 bar) to afford the polymer. GPCanalysis for the polymer product after washing with 250 ml methanol/10ml HCl (37%) and soxhlet extraction in ethylacetate (50% yield) showsM_(n)=25*10³ g/mol, M_(w)=35*10³ g/mol, P50% yield D=1.4 (THF, PPPstandard).

1. A polymer comprising repeating unit(s) of the following formula

wherein R¹, R², R³, R⁴, R⁵ and R⁶ are independently of each otherhydrogen, F, SiR¹⁰⁰R¹⁰¹R¹⁰², or an organic substituent, or R¹ and R³, R⁴and R², R³ and R⁴, and/or any of the substituents R⁵ and/or R⁶, whichare adjacent to each other, together form an aromatic, or heteroaromaticring, or ring system, which can optionally be substituted, m is 0, or aninteger of 1 to 3, n1 and n2 are 0, or an integer 1, or 2, R¹⁰⁰, R¹⁰¹and R¹⁰² are independently of each other C₁-C₁₈alkyl, substituted orunsubstituted C₆-C₁₈aryl, and Ar¹ and Ar² are each independently of eachother a substituted or unsubstituted arylen, or heteroarylen group. 2.The polymer according to claim 1 comprising repeating units of formulaI, wherein R¹ and R² are independently of each other H, F, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₁-C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G; R³ and R⁴are independently of each other H, F, C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₁-C₁₈perfluoroalkyl,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G; wherein at least one of R¹,R², R³ and R⁴ are different from H, each group R⁵ and R⁶ isindependently of each other in each occurrence H, halogen, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₁-C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, C₇-C₂₅aralkyl, CN, or —CO—R²⁸,m is 0, or an integer 1 to 3, D is —CO—; —COO—; —S—; —SO—; —SO₂—; —O—;—NR²⁵—; —SiR³⁰R³¹—; —POR³²—; —CR²³═CR²⁴—; or —C≡C—; and E is —OR²⁹;—SR²⁹; —NR²⁵R²⁶; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁶; —CN; or halogen, G is E,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is interrupted by D,C₁-C₁₈perfluoroalkyl, C₁-C₁₈alkoxy, or C₁-C₁₈alkoxy which is substitutedby E and/or interrupted by D, R²³, R²⁴, R²⁵ and R²⁶ are independently ofeach other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which isinterrupted by —O—; R²⁷ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkylwhich is interrupted by —O—, R²⁸ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkylwhich is interrupted by —O—, R²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkylwhich is interrupted by —O—, R³⁰ and R³¹ are independently of each otherC₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl, and R³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which issubstituted by C₁-C₁₈alkyl.
 3. The polymer according to claim 2, whereinthe polymer contains repeating units of formula

wherein R¹, R² and R³ are independently of each other C₆-C₁₂aryl, orC₂-C₁₁heteroaryl, which may optionally be substituted by one or moregroups G, and R⁴ has the meaning of R³, or is C₁-C₁₈alkyl.
 4. Thepolymer according to claim 3, wherein the polymer contains repeatingunits of formula (IIa), wherein R¹, R² and R³ are independently of eachother

wherein n₁ is 0, or an integer 1, 2, 3, or 4, n₂ is 0, or an integer 1,2, or 3, n₃ is 0, or an integer 1, 2, 3, 4, or 5, R¹⁰ and R¹¹ areindependently of each other C₁-C₂₅alkyl, or C₁-C₂₅alkoxy.
 5. The polymeraccording to claim 1 comprising repeating unit(s) of formula (IIa)

R¹ R² R³ R⁴

″ ″

″ ″ tBu

″ ″

″ ″

tBu


6. An electronic device or a component therefore, comprising the polymeraccording claim
 1. 7. An electronic device or a component according toclaim 6 which is a polymer light emitting diode, organic integratedcircuit, organic field effect transistor, organic thin film transistor,organic solar cell, thermoelectric device, electrochromic device, ororganic laser diode.
 8. Polymer light emitting diodes, comprising one ormore of the polymers according to claim 1 as electroluminescentmaterial.
 9. A compound of the formula

wherein R¹, R², R³. R⁴. R⁵ and R⁶ are independently of each otherhydrogen, F. SiR¹⁰⁰R¹⁰¹R¹⁰², or an organic substituent, or R¹ and R³, R⁴and R², R³ and R⁴, and/or any of the substituents R⁵ and/or R⁶, whichare adjacent to each other, together form an aromatic, or heteroaromaticring, or ring system, which can optionally be substituted, m is 0, or aninteger of 1 to 3, n1 and n2 are 0, or an integer 1, or 2, R¹⁰⁰, R¹⁰¹and R¹⁰² are independently of each other C₁-C₁₈alkyl, substituted orunsubstituted C₆-C₁₈aryl, and Ar¹ and Ar² are each independently of eachother a substituted or unsubstituted arylen, or heteroarylen group, X¹¹is independently in each occurrence a halogen atom, —ZnX¹²,—SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or differentand are H or C₁-C₆alkyl, wherein two radicals optionally form a commonring and these radicals are optionally branched or unbranched and X¹² isa halogen atom, or —OS(O)₂CF₃, —OS(O)₂-aryl, —OS(O)₂CH₃, —B(OH)₂,—B(OY¹¹)₂,

—BF₄Na, or —BF₄K, wherein Y¹¹ is independently in each occurrence aC₁-C₁₀alkyl group and Y¹² is independently in each occurrence—CY¹³Y¹⁴—CY¹⁵Y¹⁶—, or —CY¹⁷Y¹⁸—CY¹⁹Y²⁰—CY²¹Y²²—, wherein Y¹³, Y¹⁴, Y¹⁵,Y¹⁶, Y¹⁷, Y¹⁸, Y¹⁹, Y²⁰, Y²¹ and Y²² are independently of each otherhydrogen, or a C₁-C₁₀alkyl group, with the proviso that the followingcompounds are excluded:

Y² Y³ Y⁵ Y⁶ Y⁷ Y⁸ Y⁹ Y¹⁰ Y¹¹ Y¹² (CH₂)₅Me (CH₂)₅Me H H Br H H Br H H OMeOMe OAc H Cl OAc OAc Cl H OAc ¹⁾ ¹⁾ H ¹⁾ Br H H Br ¹⁾ H ¹⁾ ¹⁾ H Br ¹⁾ HH ¹⁾ Br H ¹⁾ ¹⁾ H H Cl H H Cl H H H H H H Cl H H Cl H H ¹⁾ ¹⁾ H H Br H HBr H H H H H Br H H H H Br H OMe OMe OAc H Cl OAc OAc H Cl OAc H H H BrH H H H Br ¹⁾O(CH₂)₅Me, or


10. A compound of the formula

wherein R¹, R², R⁵ and R⁶ are independently of each other hydrogen, F,SiR¹⁰⁰R¹⁰¹R¹⁰², or an organic substituent, or any of the substituents R⁵and/or R⁶, which are adjacent to each other, together form an aromatic,or heteroaromatic ring, or ring system, which can optionally besubstituted, m is 0, or an integer of 1 to 3, n1 and n2 are 0, or aninteger 1, or 2, R¹⁰⁰, R¹⁰¹ and R¹⁰² are independently of each otherC₁-C₁₈alkyl, substituted or unsubstituted C₆-C₁₈aryl, and Ar¹ and Ar²are each independently of each other a substituted or unsubstitutedarylen, or heteroarylen group, X¹¹ is independently in each occurrence ahalogen atom, —ZnX¹²—SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ areidentical or different and are H or C₁-C₆alkyl, wherein two radicalsoptionally form a common ring and these radicals are optionally branchedor unbranched and X¹² is a halogen atom, or —OS(O)₂CF₃, —OS(O)₂-aryl,—OS(O)₂CH₃, —B(OH)₂, —B(OY¹¹)₂,

—BF₄Na, or —BF₄K, wherein Y¹¹ is independently in each occurrence aC₁-C₁₀alkyl group and Y¹² is independently in each occurrence—CY¹³Y¹⁴—CY¹⁵Y¹⁶—, or —CY¹⁷Y¹⁸—CY¹⁹Y²⁰—CY²¹Y²²—, wherein Y¹³, Y¹⁴, Y¹⁵,Y¹⁶, Y¹⁷, Y¹⁸, Y¹⁹, Y²⁰, Y²¹ and Y²² are independently of each otherhydrogen, or a C₁-C₁₀alkyl group, with the proviso that the followingcompound is excluded

and with the further proviso that compounds of formula XIV are excluded,wherein R¹ and R² are a group of formula

wherein A is a coupling residue having phenolic OH, X¹¹ is halogen, n₁,n₂ and m are
 0. 11. A polymer according to claim 1 wherein Ar¹ and Ar²are each independently of each other a substituted or unsubstitutedphenylene, a substituted or unsubstituted naphthalene group, asubstituted or unsubstituted anthracene group, a substituted orunsubstituted diphenylanthracene group, a substituted or unsubstitutedphenanthrene group, a substituted or unsubstituted acenaphthene group, asubstituted or unsubstituted biphenylene group, a substituted orunsubstituted fluorene group, a substituted or unsubstituted carbazolylgroup, a substituted or unsubstituted thiophene group, a substituted orunsubstituted triazole group or a substituted or unsubstitutedthiadiazole group.
 12. A polymer according to claim 9 wherein Ar¹ andAr² are each independently of each other a substituted or unsubstitutedphenylene, a substituted or unsubstituted naphthalene group, asubstituted or unsubstituted anthracene group, a substituted orunsubstituted diphenylanthracene group, a substituted or unsubstitutedphenanthrene group, a substituted or unsubstituted acenaphthene group, asubstituted or unsubstituted biphenylene group, a substituted orunsubstituted fluorene group, a substituted or unsubstituted carbazolylgroup, a substituted or unsubstituted thiophene group, a substituted orunsubstituted triazole group or a substituted or unsubstitutedthiadiazole group.
 13. A polymer according to claim 10 wherein Ar¹ andAr² are each independently of each other a substituted or unsubstitutedphenylene, a substituted or unsubstituted naphthalene group, asubstituted or unsubstituted anthracene group, a substituted orunsubstituted diphenylanthracene group, a substituted or unsubstitutedphenanthrene group, a substituted or unsubstituted acenaphthene group, asubstituted or unsubstituted biphenylene group, a substituted orunsubstituted fluorene group, a substituted or unsubstituted carbazolylgroup, a substituted or unsubstituted thiophene group, a substituted orunsubstituted triazole group or a substituted or unsubstitutedthiadiazole group.